EP2452942A1 - Composé benzochalcogénoacène substitué, film mince comprenant le composé, et dispositif semi-conducteur organique comprenant le film mince - Google Patents

Composé benzochalcogénoacène substitué, film mince comprenant le composé, et dispositif semi-conducteur organique comprenant le film mince Download PDF

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EP2452942A1
EP2452942A1 EP10797180A EP10797180A EP2452942A1 EP 2452942 A1 EP2452942 A1 EP 2452942A1 EP 10797180 A EP10797180 A EP 10797180A EP 10797180 A EP10797180 A EP 10797180A EP 2452942 A1 EP2452942 A1 EP 2452942A1
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formula
compound
group
compound according
optionally
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EP2452942A4 (fr
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Yasuo Miyata
Eiji Yoshikawa
Shigehiro Yamaguchi
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Nagoya University NUC
Sumitomo Chemical Co Ltd
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Nagoya University NUC
Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to a substituted benzochalcogenoacene compound, a thin film comprising the compound and an organic semiconductor device comprising the thin film.
  • Patent Document 1 W02005/087780 [Formula 11]
  • Non-patent Document 1 Adv. Mater., 2007, 19, 3008-3011
  • the present invention can provide novel substituted benzochalcogenoacene compounds.
  • substituted benzochalcogenoacene compound (1) represented by the formula (1) (hereinafter called “substituted benzochalcogenoacene compound (1) as the case may be") of the present invention will be explained in detail.
  • Each of R 1 and R 2 independently represents a hydrogen atom, an optionally substituted C 4-30 alkyl group, an optionally substituted C 4-30 alkoxy group, an optionally substituted C 6-30 aryl group, an optionally substituted C 7-30 aralkyl group, an optionally substituted C 4-30 heteroaryl group, an optionally substituted C 5-30 heteroaralkyl group, or an optionally fluorinated C 3-30 trialkylsilyl group.
  • at least one of R 1 and R 2 is not a hydrogen atom.
  • the "C 4-30 alkyl group" in the "optionally substituted C 4-30 alkyl group” in R 1 and R 2 is any one of a linear, branched or cyclic alkyl group.
  • the specific examples of the C 4-30 alkyl group include n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, 2-hexyloctyl, n-nonyl, n-decyl, 2-hexyldecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecy
  • Examples of the substituent on the C 4-30 alkyl group include a halogen atom and a C 1-30 alkoxy group.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
  • Examples of the C 1-30 alkoxy group include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecy
  • a fluorine atom is preferable as a substituent on the C 4-30 alkyl group.
  • Examples of the fluorine atom-substituted C 4-30 alkyl group include perfluorohexyl, perfluorooctyl, perfluorodecyl, perfluorododecyl and perfluorotridecyl.
  • Examples of the "C 4-30 alkoxy group" in the "optionally substituted C 4-30 alkoxy group” in R 1 and R 2 include n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-icosyloxy, n-henicosyloxy, n-docosyloxy, n-tricosyloxy, n-tetracosyloxy, n-pentacosyloxy, n
  • C 4-20 alkoxy groups such as n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy and n-icosyloxy are exemplified.
  • substituent in the "optionally substituted C 4-30 alkoxy group” examples include halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom, a C 1-30 alkoxy group, a C 6-30 aryl group, a C 7-30 aralkyl group, a C 4-30 heteroaryl group and a C 5-30 heteroaralkyl group.
  • a hydrogen atom in the substituent may be substituted by a fluorine atom.
  • the aryl group include phenyl, 1-naphthyl and 2-naphthyl.
  • aralkyl group examples include the groups represented by the following formulae: wherein n1 represents an integer from 1 to 24, and each of n2 and n3 represents an integer from 1 to 20, respectively.
  • the heteroaryl group means an aryl group in which at least one carbon atom among carbon atoms in the aromatic ring is replaced by a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom.
  • heteroaryl group examples include thienyl, furyl, thiazolyl, thieno[3,2-b]thienyl, furoro[3,2-b]furyl, thieno[3,2-b]furyl, benzo[b]thienyl and benzo[b]furyl.
  • heteroaryl group thienyl, thiazolyl, thieno[3,2-b]thienyl, benzo[b]thienyl and benzo[b]furyl are preferable.
  • the heteroaralkyl group means a group in which at least one carbon atom in the aromatic ring in the aralkyl group is substituted by a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.
  • a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.
  • Examples of the heteroaralkyl group are represented by the following formulae: wherein n4 represents an integer from 1 to 26, n5 represents an integer from 1 to 24 and n6 represents an integer from 1 to 22. Further preferable examples are represented by the following formulae: wherein n4 represents an integer from 1 to 26, n5 represents an integer from 1 to 24 and n6 represents an integer from 1 to 22.
  • a fluorine atom is preferable as a substituent in the C 4-30 alkoxy group.
  • Examples of the substituted C 4-30 alkoxy group include perfluorohexyloxy, perfluorooctyloxy, perfluorodecyloxy, perfluorododecyloxy, perfluorotridecyloxy and methoxyethoxy.
  • aryl group in the "optionally substituted C 6-30 aryl group” in R 1 and R 2 is, preferably, a monocyclic or bicyclic aryl group, and more preferably, phenyl, 1-naphtyl and 2-naphtyl.
  • substituent in the "optionally substituted aryl group” examples include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a C 1-30 alkyl group, a C 1-30 alkoxy group, a C 6-30 aryl group, a C 7-30 aralkyl group, a C 4-30 heteroaryl group and a C 5-30 heteroaralkyl group.
  • a hydrogen atom included in the substituent may be substituted by a fluorine atom.
  • aryl group examples include phenyl, 1-naphtyl, 2-naphtyl, perfluorophenyl, 4-hexylphenyl and 4-hexyloxyphenyl.
  • Examples of the C 1-30 alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl,
  • Examples of the substituent in the "optionally substituted C 7-30 aralkyl group" in R 1 and R 2 include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a C 1-30 alkyl group, a C 1-30 alkoxy group, a C 7-30 aralkyl group, a C 4-30 heteroaryl group and a C 5-30 heteroaralkyl group.
  • the hydrogen atom in the substituent alkyl, alkoxy, aralkyl, heteroaryl or heteroaralkyl may be substituted by a fluorine atom.
  • a fluorine atom is preferable.
  • Examples of the "optionally substituted C 7-30 aralkyl group” include C 7-30 aralkyl groups represented by the following formulae: wherein n1 represents an integer from 1 to 24, and each of n2 and n3 represents an integer from 1 to 20, and substituted C 7-30 aralkyl groups represented by the following formulae: wherein each of n4 and n5 represents an integer from 1 to 24, and n6 represents an integer from 1 to 23.
  • Examples of the "optionally substituted C 4-30 heteroaryl group" in R 1 and R 2 include thienyl, furyl, thiazolyl, thieno[3,2-b]thienyl, furolo[3,2-b]furyl, thieno[3,2-b]furyl, benzo[b]thienyl and benzo[b]furyl.
  • the heteroaryl groups are exemplified by thienyl, thiazolyl, thieno[3,2-b]thienyl, benzo[b]thienyl and benzo[b]furyl, and more preferably exemplified by heteroaryl groups represented by the following formulae:
  • substituent in the "optionally substituted heteroaryl group” examples include a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, a C 1-30 alkyl group, a C 1-30 alkoxy group, a C 6-30 aryl group, a C 7-30 aralkyl group, a C 4-30 heteroaryl group and a C 5-30 heteroaralkyl group.
  • the hydrogen atom in the substituent may be substituted by a fluorine atom.
  • heteroaryl groups are exemplified by 2-thienyl, 2-thieno[3,2-b]thienyl, 2-benzo[b]thienyl, 5-fuluoro-2-thienyl, 5-hexyl-2-thienyl and 4-hexyloxy-2-thienyl.
  • substituent in the "optionally substituted C 5-30 heteroaralkyl group” examples include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a C 1-30 alkyl group, a C 1-30 alkoxy group, a C 7-30 aralkyl group, a C 4-30 heteroaryl group and a C 5-30 heteroaralkyl group.
  • the hydrogen atom in the substituent may be substituted by a fluorine atom.
  • a fluorine atom is preferable.
  • Examples of the "optionally substituted C 5-30 heteroaralkyl group” include heteroaralkyl groups represented by the following formulae: wherein n4 represents an integer from 1 to 26, n5 represents an integer from 1 to 24 and n6 represents an integer from 1 to 22.
  • the trialkylsilyl group in the "optionally fluorine atom-substituted C 3-30 trialkylsilyl group" in R 1 and R 2 is a silyl group in which the sum of the carbon atoms of alkyl groups connected to the silicon atom is 3 to 30.
  • the maximum number of the carbon atoms in one alkyl group connected to the silicon atom is 28 and the alkyl group is an optionally fluorine atom-substituted C 1-30 alkyl group.
  • the fluorine atom-substituted trialkylsilyl group means that a part or all of hydrogen atoms in the alkyl groups connected to the silicon atom are substituted by fluorine atoms.
  • trialkylsilyl group examples include trimethylsilyl, triethylsilyl, tri(i-propyl)silyl, t-butyldimethylsilyl, dimethylhexylsilyl and dimethyldodecylsilyl.
  • the bonding positions of R 1 and R 2 included in the substituted benzochalcogenoacene compound (1) of the present invention are preferably symmetrical.
  • the symmetrical positions here can be illustrated using the following formula: wherein E, R 1 and R 2 have the same meanings as described above; that is, the symmetrical positions are explained as the cases in which R 1 is connected to a and R 2 is connected to a', R 1 is connected to b and R 2 is connected to b', R 1 is connected to c and R 2 is connected to c', and R 1 is connected to d and R 2 is connected to d'.
  • Preferable case is exemplified by the case in which R 1 is connected to b and R 2 is connected to b', that is, a preferable compound is represented by the formula (2): wherein E, R 1 and R 2 have the same meanings as described above, or the case in which R 1 is connected to c and R 2 is connected to c', that is, a preferable compound is represented by the formula (3): wherein E, R 1 and R 2 have the same meanings as described above.
  • Table 10-1 Compound No. E 1 E 2 E 3 R 1 R 2 166 S S S 167 S S S 168 S S S 169 S S S 170 S S S 171 S S S S 172 S S S 173 S S S 174 S S S 175 S S S S Dashed line indicates a chemical bond.
  • Table 10-2 Compound No. E 1 E 2 E 3 R 1 R 2 176 S S S 177 S S S 178 S S S S 179 Se Se Se n-C 6 H 13 180 S S S 181 S S S 182 S Se S 183 S Se S 184 S Se S Dashed line indicates a chemical bond.
  • substituted benzochalcogenoacene compounds (1) a compound is preferable in which three of E's in the benzochalcogenoacene compound (1) are all sulfur atoms.
  • substituted benzochalcogenoacene compounds (1) having the following numbers in the above tables are preferably exemplified:
  • the substituted benzochalcogenoacene compound (1) of the present invention is excellent in the solubility in the organic solvent, therefore, its handling is easy and its purification is easily carried out.
  • a thin film can be also formed by dissolving the substituted benzochalcogenoacene compound (1) in the organic solvent, applying the solution and drying it.
  • the thin film can be easily formed by the applying and film-forming process to be described hereinafter, since the substituted benzochalcogenoacene compound (1) is excellent in the solubility.
  • the substituted benzochalcogenoacene compound (1) can provide a thin film showing high carrier mobility.
  • a process for producing the substituted benzochalcogenoacene compound (1) is described below.
  • a diacetylene compound which is represented, for example, by the formula (5-1) (hereinafter optionally described as a "compound (5-1)”): (wherein R 1 and R 2 represent the same meanings as described above, and X represents a halogen atom, preferably, a bromine atom), and subsequently, after dimetallation by a halogen-metal exchange reaction using an organometallic base (hereinafter, called a "present 1st reaction"), a dichalcogen-ene compound (optionally described as a "compound (4-1)") represented by the formula (4-1): (wherein E, R 1 and R 2 represent the same meanings as described above) is obtained by working of sulfur or selenium (hereinafter, optionally described as a "present 2nd reaction”).
  • a mixture of the obtained compound (4-1) and a platinum compound such as biscyclooctadienyl platinum (Pt(COD) 2 ) or a copper compound such as a copper powder is heated in the absence of a solvent (hereinafter, optionally described as a "3rd-1 reaction"), or a mixture of the obtained compound (4-1), a nickel compound such as biscyclooctadienyl nickel (Ni(COD) 2 ) and a phosphine compound is heated and stirred in the presence of a solvent (optionally described as a "3rd-2 reaction").
  • organometallic bases used in the present 1st reaction are exemplified by organolithium compounds such as methyllithium (MeLi), n-butyllithium (n-BuLi), sec-butyllithium (sec-BuLi) and tert-butyllithium (t-BuLi) and an organomagnesium compound such as an alkylgrignard compound.
  • organolithium compound is preferable as the organometallic base.
  • butyllithium (BuLi) can be used, and more preferably, t-butyl lithium (t-BuLi) can be used.
  • the amount of the organometallic base to be used based on 1 mole of the compound (5-1) is, for example, in the range of 4 to 20 moles (in the range of 2 to 10 equivalents to 1 equivalent of a halogen atom), preferably in the range of 6 to 14 moles (in the range of 3 to 7 equivalents to 1 equivalent of a halogen atom), more preferably, in the range of 7 to 10 moles (in the range of 3.5 to 5 equivalents to 1 equivalent of the halogen atom).
  • the amount of the organometallic base used is 4 moles or more, the unreacted amount of the compound (5-1) is reduced and the yield of the obtained compound (4-1) tends to increase.
  • the amount used is 20 moles or less, a progress of a side reaction is suppressed and a purification of the compound (4-1) tends to become easy.
  • the present 1st reaction and the succeeding 2nd reaction are preferable to be carried out in the presence of a solvent.
  • the solvent used is selected from those which do not remarkably prevent the present 1st and 2nd reactions.
  • aliphatic hydrocarbon solvents such as pentane, hexane and heptane, aromatic solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether and tetrahydrofuran (THF) and the mixtures of 2 or more selected among them are used.
  • a preferable solvent is the ether solvent.
  • the present 1st reaction is carried out at temperatures of, for example, -20°C or lower, preferably, -40°C or lower, more preferably, -60°C or lower.
  • the reaction time of the present 1st reaction can be controlled by the kind of organometallic bases or the solvents or by the reaction temperature, and the reaction time is in the range around from 10 minutes to 5 hours.
  • the present second reaction is carried out.
  • a sulfur (or selenium) may be used as purchased or may be added as a solution or a suspension dissolved or suspended in the solvent used in the present 1st reaction.
  • the reaction temperature may be kept at a similar temperature to the present 1st reaction or may be heated in the temperature range which does not exceed the boiling point of the solvent used. Preferably, heating is carried out to reach the temperature range of 0 to 40°C, and subsequently, the temperature is kept in the same range.
  • the reaction time is, for example, from 30 minutes to 72 hours.
  • a crystalline, powder or colloidal sulfur (or selenium) can be used as the sulfur or selenium to be used in the present 2nd reaction.
  • the amount of the sulfur or selenium used may be, for example, in the range of 4 to 20 moles, preferably, in the range of 6 to 14 moles, more preferably, in the range of 7 to 10 moles based on 1 mole of the compound (1-5). It is preferable to use the sulfur (or selenium) in the amount of 4 moles or more, since the yield of the compound (4-1) tends to increase in the molar range.
  • the sulfur (or selenium) in the amount of 20 moles or less, since, in the molar range, a progress of a side reaction can be inhibited and a purification of the compound (4-1) tends to become easy.
  • a solvent in the reaction mixture is optionally evaporated.
  • an alkaline water solution such as a sodium hydroxide water solution or a potassium hydroxide water solution is added, and the obtained compound (4-1) is extracted.
  • the solvent used in the present 1st and 2nd reactions is water, the solvent can be used directly as an extraction solvent.
  • a halogenated hydrocarbon solvent such as dichloromethane or chloroform as the extraction solvent.
  • the water phase is separated, then, to the water phase, a water solution of a hexacyanoferrate (III) salt such as potassium ferrycyanide is added, and subsequently, the compound (4-1) is extracted from the water phase by using an organic solvent such as said extraction solvent.
  • a hexacyanoferrate (III) salt such as potassium ferrycyanide
  • a copper compound or a platinum compound can be used in an amount of, for example, 0.5 to 20 moles, preferably 1 to 10 moles, more preferably 2 to 7 moles based on 1 mole of the compound (4-1).
  • An example of the copper compound is a copper powder and an example of the platinum compound is biscyclooctadienyl platinum (Pt(COD) 2 ).
  • a reaction temperature of the present 3rd-1 reaction is, for example, from 150 to 400°C, preferably, from 200 to 370°C.
  • a reaction temperature of the present 3rd-1 reaction is within 1 hour, preferably, within 30 minutes.
  • the reaction temperature is lowered to room temperature, and insoluble impurities are filtered off by using an organic solvent such as chloroform or dichloromethane which can dissolve the substituted benzochalcogenoacene compound (1).
  • the filtrate is concentrated and optionally followed by application of column chromatography, recrystallization, etc. to result in the production of the substituted benzochalcogenoacene compound (1).
  • a zero valent nickel compound such as biscyclooctadienyl nickel (Ni(COD) 2 ) is preferable as a nickel compound used in the present 3rd-1 reaction.
  • the zero valent nickel compound may be formed in-situ by reduction of a two valent nickel compound such as bisacetylacetonato nickel (Ni(acac) 2 ) with a reducing agent such as diisobutylaluminum hydride.
  • the amount of the nickel compound used is, for example, in a range of 0.5-5 moles, and preferably in a range of 0.7-3 moles based on 1 mole of the compound (4-1).
  • Examples of a phosphine compound include triphenylphosphine, tricyclohexylphosphine, tri(o-tolyl)phosphine, trimethylphosphine, tri-t-butylphosphine, 1,2-(diphenylphosphino)ethane, 1,3-(diphenylphosphino)propane, 1,4-(diphenylphosphino)butane and 1,1-bis(diphenylphosphino)ferrocene.
  • triphenylphosphine is preferable.
  • the amount of the phosphine compound used is, for example, in a range of 0.5-20 moles of the phosphine compound, preferably, in a range of 0.7-10 moles based on 1 mole of the nickel compound.
  • Examples of a solvent used in the present 3rd-2 reaction include an aliphatic hydrocarbon solvent such as pentane, hexane and heptane, an aromatic hydrocarbon solvent such as benzene, toluene and xylene, and a halogenated hydrocarbon solvent such as dichloromethane and chloroform. These solvents can be use alone or in a mixture of 2 or more of them.
  • the aromatic hydrocarbon solvent is preferable, and toluene is more preferable as the solvent.
  • the reaction temperature of the present 3rd-2 reaction is, for example, in a range from 10°C to a boiling point or lower of the solvent.
  • the reaction time of the present 3rd-2 reaction is preferably within 72 hours depending on the reaction temperature.
  • Table 47-1 Compound No. X 1 X 2 R 1 R 2 1306 Br Br 1307 Br Br 1308 Br Br 1309 Br Br 1310 Br Br 1311 Br Br 1312 Br Br 1313 Br Br 1314 Br Br 1315 Br Br Dashed line indicates a chemical bond.
  • Table 47-2 Compound No. X 1 X 2 R 1 R 2 1316 Br Br 1317 Br Br 1318 Br Br 1319 Br Br Br n-C 6 H 13 1320 Br Br 1321 Br Br 1322 Br 1323 Br Br 1324 Br Dashed line indicates a chemical bond.
  • Table 48-1 Compound No. X 1 X 2 R 1 R 2 1325 Br Br 1326 Br Br 1327 Br Br 1328 Br Br 1329 Br Br 1330 Br Br 1331 Br Br 1332 Br Br 1333 Br Br 1334 Br Br Dashed line indicates a chemical bond.
  • Table 48-2 Compound No. X 1 X 2 R 1 R 2 1335 Br Br 1336 Br Br 1337 Br Br 1338 Br Br 1339 Br Br 1340 Br Br 1341 Br 1342 Br 1343 Br Br Dashed line indicates a chemical bond.
  • Table 54-1 Compound No. X 1 X 2 R 1 R 2 1446 Br Br 1447 Br Br 1448 Br Br 1449 Br Br 1450 Br Br 1452 Br Br 1453 Br Br Dashed line indicates a chemical bond.
  • Table 54-2 Compound No. X 1 X 2 R 1 R 2 1455 Br Br 1456 Br Br 1457 Br Br 1458 Br Br 1459 Br Br 1460 Br Br Dashed line indicates a chemical bond.
  • Table 58-1 Compound No. X 1 X 2 R 1 R 2 1505 Br Br 1506 Br Br 1507 Br Br 1508 Br Br 1509 Br Br 1510 Br Br 1511 Br Br 1512 Br Br 1513 Br Br Dashed line indicates a chemical bond.
  • Table 58-2 Compound No. X 1 X 2 R 1 R 2 1514 Br Br 1515 Br Br 1516 Br Br 1517 Br Br 1518 Br Br 1519 Br Br 1520 Br Br 1521 Br Dashed line indicates a chemical bond.
  • Table 59-1 Compound No. X 1 X 2 R 1 R 2 1522 Br Br 1523 Br Br 1524 Br Br 1525 Br Br 1526 Br Br 1527 Br Br 1528 Br Br 1529 Br Br 1530 Br Br Dashed line indicates a chemical bond.
  • Table 59-2 Compound No.
  • Table 84-1 Compound No. E 1 E 2 E 3 R 1 R 2 736 S S S 737 S S S 738 S S S 739 S S S 740 S S S 741 S S S 742 S S S 743 S S S 744 S S S 745 S S S Dashed line indicates a chemical bond.
  • Table 84-2 Compound No. E 1 E 2 E 3 R 1 R 2 746 S S S 747 S S S 748 S S S 749 Se Se Se n-C 6 H 13 750 S S S 751 S S S 752 S Se S 753 S Se S 754 Se S Se Dashed line indicates a chemical bond.
  • Table 85-1 Compound No. E 1 E 2 E 3 R 1 R 2 755 S S S 756 S S S 757 S S S 758 S S S 759 S S S 760 S S S S 761 S S S 762 S S S 763 S S S 764 S S S Dashed line indicates a chemical bond.
  • Table 85-2 Compound No. E 1 E 2 E 3 R 1 R 2 765 S S S 766 S S S 767 S S S 768 S S S 769 S S S S 770 S S S 771 S S S 772 S S S 773 S S S Dashed line indicates a chemical bond.
  • the compound (5-1) used for the present 1st reaction is described for the case that R 1 and R 2 are the same kinds (hereinafter, optionally described as R) as follows. That is, the compound (5-1) can be produced by the so-called Glaser Reaction, the Eglinton Coupling or the Hay Coupling (preferably, the Hay Coupling utilizing a copper compound such as copper iodide) by using, for example, a compound represented by the formula (6-1): (wherein R represents the same meaning as R 1 and R 2 , and X represents a halogen atom, preferably, a bromine atom).
  • the Hay Coupling can be carried out, for example, in the presence of N,N,N',N'-tetramethyethylnediamine (TMEDA) and a copper compound such as copper iodide according to the reaction formula below.
  • TEDA N,N,N',N'-tetramethyethylnediamine
  • a copper compound such as copper iodide according to the reaction formula below.
  • the compound of the formula (6-1) can be produced, for example, by the process comprising steps of:
  • Table 112 Compound No. X 1 R 1 1711 Br n-C 4 H 9 1712 Br s-C 4 H 9 1713 Br n-C 5 H 11 1714 Br 1715 Br n-C 6 H 13 1716 Br 1717 Br 1718 Br n-C 7 H 15 1719 Br n-C 8 H 17 1720 Br n-C 9 H 19 1721 Br n-C 10 H 21 1722 Br 1723 Br n-C 11 H 23 1724 Br n-C 12 H 25 1725 Br n-C 13 H 27 Dashed line indicates a chemical bond.
  • Table 121-1 Compound No. X 1 R 1 1876 Br 1877 Br 1878 Br 1879 Br 1880 Br 1881 Br 1882 Br 1883 Br 1884 Br Dashed line indicates a chemical bond.
  • Table 121-2 Compound No. X 1 R 1 1885 Br 1886 Br 1887 Br 1888 Br 1889 Br 1890 Br 1891 Br 1892 Br 1893 Br 1894 Br Dashed line indicates a chemical bond.
  • Table 122-1 Compound No. X 1 R 1 1895 Br 1896 Br 1897 Br 1898 Br 1899 Br 1900 Br 1901 Br 1902 Br 1903 Br 1904 Br Dashed line indicates a chemical bond.
  • Table 122-2 Compound No. X 1 R 1 1905 Br 1906 Br 1907 Br 1908 Br 1909 Br 1910 Br 1911 Br 1912 Br 1913 Br Dashed line indicates a chemical bond.
  • Table 128-1 Compound No. X 1 R 1 2016 Br 2017 Br 2018 Br 2019 Br 2020 Br 2022 Br 2023 Br Dashed line indicates a chemical bond.
  • Table 128-2 Compound No. X 1 R 1 2025 Br 2026 Br 2027 Br 2028 Br 2029 Br 2030 Br Dashed line indicates a chemical bond.
  • Table 132-1 Compound No. X 1 R 1 2075 Br 2076 Br 2077 Br 2078 Br 2079 Br 2080 Br 2081 Br 2082 Br 2083 Br Dashed line indicates a chemical bond.
  • Table 132-2 Compound No. X 1 R 1 2084 Br 2085 Br 2086 Br 2087 Br 2088 Br 2089 Br 2090 Br 2091 Br Dashed line indicates a chemical bond.
  • Table 133-1 Compound No. X 1 R 1 2092 Br 2093 Br 2094 Br 2095 Br 2096 Br 2097 Br 2098 Br 2099 Br 2100 Br Dashed line indicates a chemical bond.
  • Table 133-2 Compound No. X 1 R 1 2101 Br 2102 Br 2103 Br 2104 Br -Si(CH 3 ) 3 2105 Br -Si(C 2 H 5 ) 3 2106 Br -Si(i-C 3 H 7 ) 3 2107 Br -Si(CH 3 ) 2 (t-C 4 H 9 ) 2108 Br -Si(CH 3 ) 2 (n-C 6 H 13 ) 2109 Br -Si(CH 3 ) 2 (n-C 12 H 25 ) Dashed line indicates a chemical bond.
  • a process for producing the substituted benzochalcogenoacene compound (1) in the case that R 1 and R 2 are the same or different kinds, is exemplified by a process according to the description of the non-patent literature 1 ( Advanced Materials, 19, 3008-3011 (2007 )). That is, the process comprises the sequential steps of:
  • a thin film of the present invention comprises the substituted benzochalcogenoacene compound (1).
  • the thin film shows high carrier mobility. Therefore, the thin film is suitable for a material for an organic semiconductor device having the thin film as an active organic semiconductor layer.
  • the organic semiconductor device of the present invention comprises the thin film of the present invention.
  • Examples of the organic semiconductor device of the present invention include an organic transistor, an electroluminescence device and a solar cell.
  • the organic transistor of the present invention can be used, for example, in an electronic paper, a flexible display, an IC tag and a sensor.
  • the formation process of the thin film of the present invention is exemplified by the applying and film-forming process.
  • the applying and film-forming process means the film-forming process which comprises the steps of dissolving the substituted benzochalcogenoacene compound (1) in a solvent and applying the obtained solution composition on a substrate or an insulating layer.
  • the coating process include a casting process, a dip coat process, a die coater process, a roll coater process, a bar coater process, an ink jet process, a screen printing process, an offset printing process and a microcontact printing process. These processes can be used alone or in combination of two or more of these processes.
  • a relevant solvent which is used for the preparation of the above solution composition can be selected properly depending on the kind of the substituted benzochalcogenoacene compound to be applied.
  • the solvent include an aromatic hydrocarbon solvent such as benzene, toluene, xylene, chlorobenzene and o-dichlorobenzene, a halogenated hydrocarbon solvent such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1',2,2'-tetrachloroethane, tetrachlorocarbon, an ether solvent such as tetrahydrofuran and dioxane, and an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane and cyclohexane.
  • the concentration of the substituted benzochalcogenoacene compound (1) in the solution composition is 0.01-50 wt%, preferably, 0.01-10 wt%, more preferably, 0.1-5 wt%. Additionally, within the range where carrier mobility is not damaged remarkably, additives such as an antioxidant or a stabilizer can be contained in the solution composition.
  • the solution composition can be obtained by dissolving the substituted benzochalcogenoacene compound (1) in the solvent at temperatures of, for example, 10-200°C, preferably, 20-150°C.
  • a thin film can be formed on the substrate or the insulating layer by eliminating the solvent contained in the coated film.
  • a naturally drying treatment, a heating treatment, a reduced pressure treatment, a draught drying treatment and a combination thereof can be adopted.
  • the naturally drying treatment or the heating treatment are preferable from the point of easy operation.
  • the operation condition for the treatment is described as still-standing under the atmosphere or heating of the substrate on a hot plate (for example, at 40-250°C, preferably, 50-250°C).
  • the thin film of the present invention can be formed by the applying and film-forming process by using also a dispersion of the substituted benzochalcogenoacene compound (1) in the solvent, and in this case, the process can be easily carried out by reading the solution composition as the dispersion composition.
  • the thin film of the present invention can be formed by a simple method such as the applying and film-forming process as described above.
  • Another different example of the thin film forming process of the present invention is a thin film forming process under vacuum such as a vacuum deposition process, a sputtering process, a CVD process and a molecular beam epitaxial process.
  • the substituted benzochalcogenoacene compound is heated in a crucible or a metal boat under vacuum, and the evaporated organic semiconductor material is deposited on the substrate or the insulating material.
  • a degree of vacuum when deposition occurs is, generally, 1x10 -1 Pa or lower, preferably, 1x10 -3 Pa or lower.
  • a substrate temperature when deposition occurs is, generally, 0°C -300°C, preferably, 20°C -200°C.
  • a deposition speed is, for example, 0.001nm/sec - 10nm/sec, preferably, 0.01nm/sec - 1nm/sec.
  • a thickness of the thin film comprising the substituted benzochalcogenoacene compound (1) obtained by the above applying and film-forming process or the above vacuum process is controllable, for example, depending on a device structure of the organic transistor, and the film thickness is preferably 1nm-10 ⁇ m, more preferably, 5nm-1 ⁇ m.
  • An example of the organic transistor of the present invention is the organic field effect transistor (OFET).
  • the structure of the organic field effect transistor is, for example, generally provided with a source electrode and a drain electrode close to the organic semiconductor active layer consisting of the thin film of the present invention, and further provided with a gate electrode across an insulator layer (a dielectric layer) close to the organic semiconductor active layer.
  • Examples of the device structure include the followings:
  • materials constituting the source electrode, the drain electrode and the gate electrode are not limited specifically as far as the materials are electrically conducting materials such as platinum, gold, silver, nickel, chromium, copper, iron, tin, lead antimony, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, molybdenum oxide, tungsten, antimony tin oxide, indium tin oxide (ITO), zinc doped with fluorine, zinc, carbon, graphite, a glassy carbon, a silver paste and carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, a sodium-potassium alloy, magnesium, lithium, aluminum, a magnesium/ copper mixture, a magnesium/silver mixture, a magnesium/
  • electrically conducting materials such as platinum, gold, silver, nickel, chromium, copper, iron,
  • conductive polymers whose conductivity is improved by doping, etc. are also suitably used.
  • conductive polymers include a conductive polyaniline, a conductive polypyrrole, a conductive polythiophene and a complex between polyethylenedioxythiophene and polystyrene sulfonic acid.
  • the conductive materials which have a low electric resistance at the contact face with the semiconductor layer are preferable. These conductive materials may be used alone or in a mixture of two or more kinds.
  • a film thickness of the electrode varies depending on the material, and the thickness is, preferably, 0.1nm-10 ⁇ m, further preferably, 0.5nm-5 ⁇ m, and more preferably, 1nm-3 ⁇ m.
  • the film thickness may be larger than the above values.
  • the source electrode and the drain electrode used in the organic transistor of the present invention may undergo a surface treatment.
  • the surface treatment of the electrode surface contacting with the thin film (the organic semiconductor active layer) of the present invention is preferable, since the surface treatment tends to improve the transistor performances of the organic transistor comprising the thin film.
  • An example of the surface treatment is a modification process of the electrode surfaces mentioned above by dipping the electrodes in an alcohol solution of, for example, a saturated hydrocarbon compound having a thiol group such as 1-octylthiol, 1-perfluorooctylthiol, 1-octadecylthiol and 1-perfluorooctadecylthiol, an aromatic compound having a thiol group such as benzenethiol and perfluorobenzenethiol, and a heteroaromatic compound having a thiol group such as thienylthiol and perfluoro-thienylthiol.
  • a saturated hydrocarbon compound having a thiol group such as 1-octylthiol, 1-perfluorooctylthiol, 1-octadecylthiol and 1-perfluorooctadecylthiol, an aromatic compound having a thi
  • the electrode can be manufactured by various methods using above raw materials. Specifically, a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method and a sol-gel method are exemplified. At or after the film-forming, it is preferable to carry out patterning, optionally.
  • the patterning can be carried out by using various methods. Specifically, a photolithography method which combines a patterning and an etching of the photoresist is exemplified. In addition, soft-lithography methods such as an inkjet printing, a screen printing, an offset printing and an anastatic printing are exemplified. These methods can be used for the patterning, alone or in combination of two or more of them.
  • Inorganic oxides, inorganic nitrides and organic compounds can be exemplified as materials for the insulating films.
  • examples of inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, strontium barium titanate, barium titanate zirconate, lead titanate zirconate, lanthanum lead titanate, strontium titanate, barium titanate, magnesium barium fluoride, bismuth titanate, bismuth strontium titanate, bismuth strontium tantalite, bismuth niobate tantalite and yttrium trioxide.
  • Silicon oxide, aluminum oxide, tantalum oxide and titanium oxide are preferable.
  • the organic compounds include polyimide, polyamide, polyester, polyacrylate, a photo-curable resin obtained by photo-radical polymerization or photo-cationic polymerization, a copolymer comprising an acrylonitrile component, polyvinylphenol, polyvinylalcohol, a novolak resin and cyanoethylpullulan.
  • Polyimide, polyvinylphenol and polyvinylalcohol are preferable.
  • These materials for the insulating layer can be used alone or in combination of two or more of them.
  • a thickness of the insulating layer varies depending on the material, and the thickness is, preferably, 0.1nm-100 ⁇ m, further preferably, 0.5nm-50 ⁇ m, and more preferably, 5nm-10 ⁇ m.
  • the insulating layer can be formed by various methods. Specifically, a spin coating, a spray coating, a dip coating, a cast, a bar coating, a blade coating, a screen printing, an offset printing, an inkjet and dry process methods such as a vacuum deposition, a molecular beam epitaxial growth method, an ion cluster beam method, an ion plating method, a sputtering method, an atmospheric plasma method and a CVD method are exemplified. In addition, a sol-gel method and a method in which an oxide film is formed on a metal substrate such as an alumite on aluminum or a thermal oxide film of silicon are exemplified.
  • the materials of the substrate include glass, paper, quartz, ceramic and a resin sheet.
  • materials for the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polyetherimide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC) and cellulose acetate propionate (CAP).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PES polyether sulfone
  • polyetherimide polyether ether ketone
  • polyphenylene sulfide polyarylate
  • polyimide polycarbonate
  • PC cellulose triacetate
  • CAP cellulose acetate propionate
  • the thickness of the substrate is, preferably, 1 ⁇ m-10mm, more preferably, 5 ⁇ m-5mm.
  • a surface treatment may be carried out on the insulating layer and the substrate.
  • the transistor performance of the organic transistor can be improved.
  • the surface treatment is exemplified specifically by a hydrophorbic treatment by hexamethyldisilazane, octadecyltrichlorosilane, octyltrichlorosilane and phenetyltrichlorosilane, an acid treatment by hydrochloric acid, sulfuric acid and an aqueous hydrogen peroxide solution, an alkaline treatment by sodium hydroxide, potassium hydroxide, calcium hydroxide and an aqueous ammonia, an ozone treatment, a hydrogen fluoride treatment, a plasma treatment such as oxygen and argon, a film-forming treatment of Langmuir-Brodgett film, a thin-film forming treatment of other insulator and semiconductor films, a mechanical treatment, an electric treatment such as corona discharge and a rubbing treatment using fibers.
  • a hydrophorbic treatment by hexamethyldisilazane
  • octadecyltrichlorosilane
  • Processes for the surface treatment are exemplified by a vacuum deposition process, a sputtering process, a coating process, a printing process and a sol-gel process.
  • a protective film consisting of resins or inorganic compounds may be laminated on the organic semiconductor active layer.
  • the formation of the protective film inhibits influences from the outer circumstances to result in stabilization of the transistor drive.
  • the thin film of the present application exhibits a high carrier-mobility, since it comprises the substituted benzochalcogenoacene compound (1). Therefore, the thin film of the present application is useful as the organic semiconductor active layer in the organic transistor, and the organic transistor having the organic semiconductor active layer comprising the thin film of the present invention exhibits excellent transistor performances and is useful for the organic semiconductor device.
  • the organic phase was extracted and dried with sodium sulfate, followed by condensation by the evaporator to give an oil product.
  • the oil product was purified by a silica gel column to give 2-bromo-4-hexylaniline (35.63g, 139.1mmol, yield 48.8%).
  • reaction mixture was refluxed for 20 minutes by heating, and then cooled to the room temperature. Subsequently, the reaction mixture was poured into an aqueous solution (water 450mL) of sodium sulfite (22.5g, 216.2mmol). Ethyl acetate was added to the reaction mixture, then, the organic phase was extracted, dried with magnesium sulfate and condensed by the evaporator to result in the formation of a brown oil (28.15 g) which contains 2-bromo-4-hexyl-1-iodobenzene as a main component (76.7mmol, yield 76.7%).
  • the compound [1145] (10.6g, 20mmol) obtained in the Preparation example 4 was dissolved in THF 200mL, and to this solution, under nitrogen atmosphere at -78°C, a 1.59M pentane solution (62.9mL, 100.0mmol) of t-BuLi was added in drops. After stirring at -78°C for 1 hour, a sulfur powder (3.2g, 100.0mmol) was added by small pieces, and subsequently, the temperature was slowly raised to room temperature and stirring was continued for 2 hours. A 1M sodium hydroxide solution (300mL) and K 3 Fe (CN) 6 (32.9g, 100.0mmol) were added, and after stirring for 1 hour at room temperature, chloroform was added to extract the organic phase.
  • Example 3 Formation of a thin film consisting of the compound [5] by vacuum deposition method and manufacture of an organic transistor having the thin film>
  • Electrodes of chromium in 3nm and gold in 50nm deposited in this order were formed by the vapor deposition method using a metal mask on the substrate laminated with hexamethyldisilazane by spin coating over n-doped silicon wafer having a thermally oxidized SiO 2 film.
  • Each of a channel width and a channel length of the electrode formed was 2000 ⁇ m and 20 ⁇ m, respectively.
  • the compound [5] synthesized in Example 1 and purified by sublimation was put into a quartz crucible, and the crucible was heated to form a thin film consisting of the compound [5] by the vacuum deposition method.
  • the degree of vacuum in the apparatus chamber used for the vacuum deposition method was 1 ⁇ 10 -4 pascal or lower, and the temperature of the substrate was in a range from room temperature (24°) to 80°C or lower.
  • the thickness of the thin film was about 200nm.
  • each of L and W represents a channel length and a channel width of the organic transistor, respectively
  • Ci represents an electrostatic capacitance per unit area of an insulating layer for the gate electrode (hereinafter, optionally described as a gate insulating film)
  • Vg represents a gate voltage
  • Vt represents a threshold value voltage of the gate voltage.
  • the saturated field-effect mobility ⁇ of the carrier in the organic transistor having the thin film consisting of the compound [5] and manufactured was calculated by using the formula (a), and the following results were obtained. That is, the saturated field-effect mobility of the carrier (carrier mobility) in the organic transistor having the thin film consisting of the compound [5] and manufactured at a substrate temperature of 60°C was 1.6cm 2 /Vs. In addition, the ratio of the drain currents Ids at the gate voltages of 0 V and - 50 V (hereinafter, optionally described as on/of ratio) at the drain voltage Vd of -50 V was 10 7 .
  • the solution composition containing the compound [5] in 0.5 wt% concentration was prepared by dissolving the compound [5] manufactured in Example 1 in tetrahydrofuran. This solution composition was applied on the n-doped silicon wafer having a thermally oxidized SiO 2 film treated with hexamethyldisilazane using a spin coat method, and thus, the thin film consisting of the compound [5] was formed. In addition, the formed thin film was kept at 80°C for 30 minutes. The thickness of the thin film was about 30nm.
  • Example 5 On the thin film obtained in Example 5, a molybdenum oxide layer and successively a gold layer were formed using a metal mask by the vacuum deposition method, and thus, a source electrode and a drain electrode were formed.
  • each of a channel width and a channel length of the organic TFT obtained by forming the source electrode and the drain electrode was 2000 ⁇ m and 20 ⁇ m, respectively.
  • the organic transistor having the thin film comprising the compound [5] as shown in Fig. 2 was manufactured.
  • Example 6 The electric performances of the organic transistor manufactured in Example 6 were also measured similarly to Example 4. The results showed that each of the field-effect mobility of the carrier (carrier mobility) and the on/off ratio was 0.3cm 2 /Vs and 10 7 , respectively.
  • Example 8 Manufacture of the organic transistor having a thin film consisting of the compound [14] >
  • a source electrode and a drain electrode in the sequence of chromium and gold starting from the thermally oxidized SiO 2 film having a channel width of 2000 ⁇ m and a channel length of 20 ⁇ m were formed.
  • the substrate was washed with acetone in ultrasonic bath for 10 minutes and irradiated by an ozone UV for 20 minutes. Then, the substrate surface was silanized by dipping the substrate in the toluene diluent solution of phenylethyltrichlorosilane for 2 minutes.
  • the surface of the Au electrode formed on the substrate was modified by dipping the substrate in the isopropyl alcohol diluent solution of perfluorobenzene thiol for 2 minutes, and thus, the transistor substrate was manufactured. Then, the compound [14] synthesized in Example 2 was put into the crucible, the crucible was heated, and thus, by the vacuum deposition method, a thin film consisting of the compound [14] was formed on the transistor substrate. A vacuum degree in the apparatus chamber used for the vacuum deposition was 1 ⁇ 10 -4 pascal or less and the substrate temperature was 80°C. A thickness of the thin film was about 100nm.
  • a thin film was formed by the vacuum deposition method according to the same procedure as Example 3 except using the compound C-1 represented by the above formula and disclosed in the patent document 1, then followed by manufacturing the organic transistor having the thin film.
  • the electric performances of the obtained organic transistor were measured according to Example 4, and the results showed that the carrier mobility and the on/off ratio of the obtained organic transistor were 10 -5 cm 2 /Vs and 10 3 , respectively.
  • Example 12 Preparation of the compound [14], formation of a thin film consisting of the compound [14] by the applying and film-forming process, and manufacture and measurement of a transistor having the thin film>
  • the compound [14] (which means the compound No. 41 in Table 2) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-pentyloxyaniline is used instead of 4-dodecylaniline.
  • a transistor substrate is prepared according to a similar procedure to Example 8
  • an organic transistor having the thin film is produced according to a similar procedure to Example 10.
  • a high value of the carrier mobility can be obtained.
  • the compound [155] (which means the compound No. 155 in Table 9) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-(4-phenylbutul)aniline is used instead of 4-dodecylaniline.
  • a transistor substrate is prepared according to a similar procedure to Example 8
  • an organic transistor having the thin film is produced according to a similar procedure to Example 10.
  • a high value of the carrier mobility can be obtained.
  • the compound [222] (which means the compound No. 222 in Table 13) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 3-octylaniline is used instead of 3-octylaniline in Preparation example 1.
  • a transistor substrate is prepared according to a similar procedure to Example 8
  • an organic transistor having the thin film is produced according to a similar procedure to Example 10.
  • a high value of the carrier mobility can be obtained.
  • the compound [7] (which means the compound No. 7 in Table 1) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-(2-ethylhexyl)aniline is used instead of 4-dodecylaniline.
  • the compound [12] (which means the compound No. 12 in Table 1) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-(2-hexyldecyl)aniline is used instead of 4-dodecylaniline.
  • the compound [15] (which means the compound No. 15 in Table 1) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-tridecylaniline is used instead of 4-dodecylaniline.
  • the compound [18] (which means the compound No. 18 in Table 2) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-hexadecylaniline is used instead of 4-dodecylaniline.
  • the compound [42] (which means the compound No. 42 in Table 2) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-(2-hexyloctyl)aniline is used instead of 4-dodecylaniline.
  • the compound [84] (which means the compound No. 84 in Table 4) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-(4'-hexylphenyl)aniline is used instead of 4-dodecylaniline.
  • the compound [97] (which means the compound No. 97 in Table 5) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-(2-(5-hexyl)thienyl) aniline is used instead of 4-dodecylaniline.
  • the compound [205] (which means the compound No. 205 in Table 12) can be obtained according to similar procedures to Preparation examples 7 and 8 and Example 2 except that 4-[(2-benzo[b]thieno)octyl]aniline is used instead of 4-dodecylaniline.
  • the compound [208] (which means the compound No. 208 in Table 12) can be obtained according to the following formula in the document: Advanced Materials, 19, 3008-3011 (2007 ):.
  • the present invention can provide the new substituted benzochalcogenoacene compound, the thin film comprising the compound and the organic semiconductor device comprising the thin film.

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EP2452942A4 (fr) 2013-01-23
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CN102574868A (zh) 2012-07-11
KR20120090939A (ko) 2012-08-17
CN102574868B (zh) 2015-01-14
TW201125871A (en) 2011-08-01
RU2012104635A (ru) 2013-08-20

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